CN105118883B - Low-cadmium CIGS-based thin-film solar cell and manufacturing method thereof - Google Patents
Low-cadmium CIGS-based thin-film solar cell and manufacturing method thereof Download PDFInfo
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- CN105118883B CN105118883B CN201510453849.9A CN201510453849A CN105118883B CN 105118883 B CN105118883 B CN 105118883B CN 201510453849 A CN201510453849 A CN 201510453849A CN 105118883 B CN105118883 B CN 105118883B
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- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 27
- 239000010409 thin film Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 35
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 10
- 238000002407 reforming Methods 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000001661 cadmium Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical group [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 64
- 230000009466 transformation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
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- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
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- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
- H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
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Abstract
The invention provides a low-cadmium CIGS-based thin-film solar cell and a manufacturing method thereof. The thin-film solar cell sequentially comprises a substrate, a back electrode, a CIGS absorption layer, a CdS layer and an upper electrode from the bottom up. Cu atoms on the surface of the CIGS absorption layer are partially replaced by Cd atoms to form a surface modified layer. The thickness of the CdS layer ranges from 20nm to 35nm. The manufacturing method comprises the following steps of (a) depositing the back electrode on the substrate; (b) depositing the CIGS absorption layer on the back electrode; (c) depositing the CdS layer on the CIGS absorption layer; and (d) depositing the upper electrode on the surface of the CdS layer. In the step c, an operation for modifying the surface of the CIGS surface is performed before the CdS layer is deposited. While the overall high CIGS cell conversion efficiency is kept, the thickness of the CdS layer is greatly lowered. The Cd content of a whole cell module is greatly reduced.
Description
Technical field
The present invention relates to technical field of thin-film solar, and in particular to a kind of low cadmium CIGS based thin film solar cells
And preparation method thereof.
Background technology
CIGS（Cu (In, Ga) Se2, abbreviation CIGS）Thin-film solar cells are high with its electricity conversion, material
Consumption is few, lightweight, can receive significant attention the features such as flexibility, and is considered as the second filial generation sun for having very much Commercial Prospect
Can battery.
The preparation section of generally CIGS thin film solaode includes：A, deposits back electrode on substrate；B, in back electrode
Upper depositing CIGS absorber layer；C, on CIGS absorbed layers CdS layer is deposited；D, on CdS layer surface Top electrode is deposited.In CIGS thin film
In solaode preparation process, needs use the CdS layer with certain environment contaminative, and it adopts chemical thought
（CBD）Thicknesses of layers prepared by technique is typically about 40-60nm or so, in being integrated into whole battery system, causes battery Cd to contain
Amount is higher, causes worry of the people to cadmium pollution, also have impact on its application prospect.Although technically can be thick by reducing CdS
Spend to reduce the Cd contents of whole component, but the reduction of CdS thickness, be greatly reduced the photoelectric conversion effect of whole battery component
Rate.Therefore in fact, at present business-like CIGS batteries CdS layer thickness general control in 50nm or so, process window is narrower, technique
Control difficulty is larger.
The content of the invention
Goal of the invention：In order to solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of low cadmium CIGS base film sun
Energy battery and preparation method thereof, the thin-film solar cells entirety Cd contents are low, technology controlling and process window is wider.
Technical scheme：
A kind of low cadmium CIGS based thin film solar cells, from the bottom to top successively include substrate, back electrode, CIGS absorbed layers,
CdS layer and Top electrode, the CIGS absorbs the Cu atoms of layer surface and is replaced to form surface reforming layer by Cd atomic components, described
The thickness of CdS layer is 20-35nm.
Preferably, the thickness of the CdS layer is 20-25nm.
The substrate is any one in glass, metal, ceramics and polymer substrate；The back electrode is that Mo is electric
Pole；The Top electrode is any one in ZnO/AZO electrodes, ZnO/ITO electrodes, AZO electrodes, ITO electrode.
A kind of preparation method of low cadmium CIGS based thin film solar cells, including following operation：
A, deposits back electrode on substrate；
B, the depositing CIGS absorber layer on back electrode；
C, on CIGS absorbed layers CdS layer is deposited；
D, on CdS layer surface Top electrode is deposited；
Before step c, to the process of CIGS modifying surfaces, concretely comprise the following steps：
（1）Prepare reaction solution A：The aqueous solution of cadmium salt is prepared, in the solution ammonia is added, with aqueous slkali pH value is adjusted
For 10.5-12, stir, obtain final product reaction solution A, room temperature is saved backup；
（2）Prepare reaction solution B：The aqueous solution of thiourea is prepared, is by volume 1 by the solution and reaction solution A：1~2
Ratio mixing, with aqueous slkali adjust pH value be 10.5-12, stir, obtain final product reaction solution B, room temperature is saved backup；
（3）The substrate that deposition obtained in operation b there are CIGS absorbed layers is placed in into chemical surface deposition（CSD）Process equipment
Heat on warm table, when underlayer temperature reaches 85-100 DEG C, by step（1）The fresh reaction solution A for preparing is at once
The substrate surface of heating is dripped to, and controls substrate surface and occur without dry, reaction 5-10min, immediately take out and remove substrate table
The unnecessary reaction solution A in face, forms surface reforming layer；
（4）By step（3）The obtained substrate for having surface reforming layer that deposits is placed on another warm table of CSD process equipments
Continue to heat, when underlayer temperature reaches 65-75 DEG C, by step（2）Obtained fresh reaction solution B drips at once the lining of heating
Basal surface, and control substrate surface occur without it is dry, react 2-8min, formed CdS film layers, substrate is taken out at once, use deionization
Water is rinsed well, then dries up substrate surface with gases at high pressure, into lower one Top electrode depositing operation.
Step（1）In, Cd in the aqueous solution of the cadmium salt2-Concentration is 3-6mmol/L, and ammonia concn is 10-20wt%,
Cd2-With NH4The mol ratio of OH is 1：10~300.
Step（2）In, the concentration of thiourea is 0.1-0.5mol/L in the aqueous solution of the thiourea.
Step（1）And step（2）In, the cadmium salt is solubility cadmium salt, is chosen in particular from CdSO4、CdCl2、CdI2With
（CH3COO）2Cd·2H2The compositionss of any one or more in 0, the aqueous slkali is 3-10mol/LNaOH solution.
To the process of CIGS absorbed layers modifying surface, the reaction being related to is that the Cd atoms in solution and CIGS inhale to the present invention
There is ion exchange in the Cu atoms for receiving layer surface, change the conductive characteristic of surface reforming layer, and Cd atoms are played in surface layer to be applied
The effect of main doping, surface reforming layer forms the PN homojunction of a shallow embedding together with substrate CIGS absorbed layer, so as to whole
Superior in quality PN junction is formed in CIGS hull cell, the high transformation efficiency of battery is maintained.Prepare on surface reforming layer very thin
CdS film layers, can solve the problem that the energy band and Lattice Matching of integral battery door, simultaneously because CdS thin-film refractive indexs value in Top electrode with
Between CIGS absorbed layers, anti-reflective effect is played.Very thin CdS film layers can significantly reduce absorption of this film layer to light, so as to increase
Plus into the incident illumination of CIGS absorbed layers, increase short circuit current, and the Cd contents of whole film layer are greatly lowered.
Beneficial effect：
1. while CIGS battery integrally high transformation efficiencies are maintained, CdS layer thickness is greatly reduced, considerably reduced
The Cd contents of whole battery component.
2. CdS layer process window has been widened, this film layer technique controlling difficulty has been reduced, has been easy to large-scale production and application.
Description of the drawings
Fig. 1 is the structural representation of the low cadmium CIGS based thin film solar cells of the present invention；
Wherein, 1, substrate；2nd, back electrode；3rd, CIGS absorbed layers；4th, surface reforming layer；5th, CdS layer；6th, Top electrode.
Specific embodiment
Below with CdSO4As a example by as cadmium salt, by way of specific embodiment, technical solution of the present invention is carried out in detail
Illustrate, but protection scope of the present invention is not limited to the embodiment.
Using range format expression value should be interpreted as in a flexible way not only include clearly include as scope
The numerical value of limit value, but also including all single numbers or subinterval for covering within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood to not only include what is clearly included
The concentration of about 0.1% to about 5%, also including the single concentration in the range of alluding to（Such as, 1%, 2%, 3% and 4%）And subinterval（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.
Embodiment 1
As shown in figure 1, a kind of low cadmium CIGS based thin film solar cells, include successively from the bottom to top substrate 1, back electrode 2,
CIGS absorbed layers 3, CdS layer 5 and Top electrode 6, the Cu atoms on the surface of CIGS absorbed layers 3 are replaced by Cd atomic components, described
The thickness of CdS layer 5 is 20nm.
The preparation method of the low cadmium CIGS based thin film solar cells, including following operation：
A, deposits back electrode on substrate；
B, the depositing CIGS absorber layer on back electrode；
C, on CIGS absorbed layers CdS layer is deposited；
D, on CdS layer surface Top electrode is deposited；
Before step c, to the process of CIGS modifying surfaces, concretely comprise the following steps：Weigh CdSO4Powder 1.6g, it is molten
In 1.276L deionized waters, stir, to CdSO4Add 224ml concentration for the ammonia of 19wt% in solution, further stir
Mix and uniformly reaction solution A is obtained.
Thiourea powder 2.85g is weighed, in being dissolved in 0.375L deionized waters, is stirred, until thiourea powder is completely dissolved,
0.75L reaction solution A are taken, is mixed with thiourea solution, it is 10.5-12 to adjust pH value with 3-10mol/LNaOH solution, and stirring is equal
It is even, obtain final product reaction solution B.
CSD will be fixed on using the substrate of the good band CIGS absorbed layers of coevaporation technique or sputtering and selenization technique process deposits
On process equipment warm table, substrate is heated, when underlayer temperature reaches 85 DEG C, solution A is titrated at once the substrate table of heating
Face（Amount of solution is 0.15ml/cm2）, 7min is reacted, substrate is taken out, excess surface reaction solution A is removed, form surface and be modified
Layer；
The substrate of obtained belt surface modified layer is put into into another warm table of CSD process equipments, temperature is controlled for 75 DEG C；Will
Obtained solution B is titrated at once the substrate surface of heating（Amount of solution is 0.15ml/cm2）, 3min is reacted, substrate is taken out, and
Deionized water is rinsed well, and with gases at high pressure substrate surface is dried up, and the CdS film layers for preparing is obtained, into lower one Top electrode
Depositing operation, and complete the preparation of whole CIGS thin film solaode.
Embodiment 2 ~ 3 be shown in Table 1 using the thickness of material quantity, reaction condition and gained CdS layer 5, remaining condition with implement
Example 1.
Table 1
。
Comparative example 1
It is, the Direct precipitation CdS layer on CIGS absorbed layers that the thickness of the CdS layer is with the difference of embodiment 1
30nm。
Comparative example 2
It is, the Direct precipitation CdS layer on CIGS absorbed layers that the thickness of the CdS layer is with the difference of embodiment 1
50nm。
I-V is tested
Solaode prepared by embodiment 1 ~ 3 and comparative example 1 ~ 2 is in standard conditions（I.e.：25 DEG C of temperature, light irradiation
Degree 1000W/m2, spectral irradiance distribution AM1.5）Under carry out I-V tests, the photoelectric transformation efficiency result for measuring is as shown in table 2.
Table 2
。
As shown in Table 2, the present invention can realize that whole battery maintains high photoelectricity while CdS layer thickness is reduced
Conversion efficiency.For the whole CIGS battery components of the present invention, Cd is primarily present in CdS layer（Account for total content more than 95%）,
It can be considered that the Cd contents in whole battery are mainly determined by the thickness of CdS film layers.And the present invention is by the way that CIGS is absorbed
The modified mode of layer surface, on the basis of high photoelectric transformation efficiency is maintained, significantly reduces CdS thicknesses of layers, realizes
The purpose of Cd contents in whole battery is greatly lowered, wherein, when the thickness of CdS layer is in 20-25nm, photoelectric transformation efficiency is more
Height, is preference.
In a word, presently preferred embodiments of the present invention, all equalizations made according to scope of the present invention patent be the foregoing is only
Change and modification, should all belong to the covering scope of patent of the present invention.
Claims (8)
1. a kind of low cadmium CIGS based thin film solar cells, include successively from the bottom to top substrate（1）, back electrode（2）, CIGS absorb
Layer（3）, CdS layer（5）And Top electrode（6）, it is characterised in that the CIGS absorbed layers（3）The Cu atoms on surface are by Cd atoms portion
Split and change to form surface reforming layer（4）, the CdS layer（5）Thickness be 20-35nm, the low cadmium CIGS based thin film solars
The preparation method of battery includes following operation：
A, deposits back electrode on substrate；
B, the depositing CIGS absorber layer on back electrode；
C, on CIGS absorbed layers CdS layer is deposited；
D, on CdS layer surface Top electrode is deposited；
Before step c, to the process of CIGS modifying surfaces, concretely comprise the following steps：
（1）Prepare reaction solution A：The aqueous solution of cadmium salt is prepared, in the solution ammonia is added, adjusting pH value with aqueous slkali is
10.5-12, stirs, and obtains final product reaction solution A, and room temperature is saved backup；
（2）Prepare reaction solution B：The aqueous solution of thiourea is prepared, is by volume 1 by the solution and reaction solution A：1 ~ 2 ratio
Example mixing, it is 10.5-12 to adjust pH value with aqueous slkali, is stirred, and obtains final product reaction solution B, and room temperature is saved backup；
（3）The substrate that deposition obtained in operation b there are CIGS absorbed layers is placed on the warm table of CSD process equipments and is heated, work as lining
When bottom temperature reaches 85-100 DEG C, by step（1）The fresh reaction solution A for preparing drips at once the substrate table of heating
Face, and control substrate surface occur without it is dry, react 5-10min, take out and remove the unnecessary reaction solution A of substrate surface at once,
Form surface reforming layer；
（4）By step（3）The obtained substrate for having surface reforming layer that deposits is placed in continuation on another warm table of CSD process equipments
Heating, when underlayer temperature reaches 65-75 DEG C, by step（2）Obtained fresh reaction solution B drips at once the substrate table of heating
Face, and control substrate surface and occur without dry, 2-8min is reacted, CdS film layers are formed, take out substrate at once, deionized water punching
Wash clean, then substrate surface is dried up with gases at high pressure, into lower one Top electrode depositing operation.
2. a kind of low cadmium CIGS based thin film solar cells according to claim 1, it is characterised in that the CdS layer（5）'s
Thickness is 20-25nm.
3. a kind of low cadmium CIGS based thin film solar cells according to claim 1, it is characterised in that the substrate is glass
Any one in glass, metal, ceramics and polymer substrate.
4. a kind of low cadmium CIGS based thin film solar cells according to claim 1, it is characterised in that the back electrode is Mo
Electrode.
5. a kind of low cadmium CIGS based thin film solar cells according to claim 1, it is characterised in that the Top electrode is
Any one in ZnO/AZO electrodes, ZnO/ITO electrodes, AZO electrodes, ITO electrode.
6. a kind of low cadmium CIGS based thin film solar cells according to claim 1, it is characterised in that step（1）In, it is described
Cd in the aqueous solution of cadmium salt2-Concentration is 3-6mmol/L, and ammonia concn is 10-20wt%, Cd2-With NH4The mol ratio of OH is 1：10~
300。
7. a kind of low cadmium CIGS based thin film solar cells according to claim 1, it is characterised in that step（2）In, it is described
The concentration of thiourea is 0.1-0.5mol/L in the aqueous solution of thiourea.
8. a kind of low cadmium CIGS based thin film solar cells according to claim 6, it is characterised in that step（1）And step
（2）In, the cadmium salt is CdSO4、CdCl2、CdI2(CH3COO)2Cd·2H2The compositionss of any one or more in 0,
The aqueous slkali is 3-10mol/LNaOH solution.
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